Manufacture of dyed products



Patented Sept. 2, 1931 UNE'E f 4:1

PATENT OFFECE RAINAIID BRIGHTMAN AND PERCY GHORLEY, OF BLACKLEY, MANCHESTER, ENGLAND,

ASSIGNORS TO BRITISH DYESTUFFS CORPORATION LIMITED, OF BLACKLEY, MAN- CHESTER, GLAND.

MANUFACTURE OF DYED PRODUCTS No Drawing. Original application filed April 16, 1928, Serial No. 270,572, and in 1927. Divided and this application. filed August 24, 1929. Serial No.

In 2120,5572, whereof the present application is a division, we have described processes of making new secondary disazo dyestuifs by combining a tetrazotized 4:4-diaminodiphenyl monodior tri-sulphide with two molecules of suitable end components, of which at least one is or contains an aminonaphthol sulphonic acid, including in this term the N-substituted derivatives thereof, directly coupled with the diaminodiphenyl sulphide residue. The other coupling component may be any of the known coupling components and either eoupling component may contain an azo group. These dyestuffs are represented by the following general formula wherein R represents a coupling component,

2 represents a coupled aminonaphthol sulphonic acid and a: is an integer greater than 0 and less than 4. These dyestuffs are valuable fordyeing animal or vegetable fiber. The components used and the conditions of coupling may be varied to produce dyestuifs having properties suitable for certain particular uses.

We have discovered that dyestuffs having the general characteristic formula as given above are especially valuable for dyeing regenerated cellulose materials in even level shades, the fiber taking the dye directly and without need of special expedients. The ordinary dye house practice may be followed, for example the methods described in U. S. Patents 1,776,802 and 1,757,501. While these references employ dyes which difit'er widely in structure from the dyes of the present invention, the manipulative procedure employed for obtaining even level shades on regenerated nitrocellulose is the same. The present invention is directed to directly dyeing regenerated cellulose materials with these dyes with production of even level shades and to the dyed material produced thereby.

Regenerated cellulose materials such as viscose silk are diflicult to dye. Most of the well known cotton dyestuffs will not produce even level shades. Although these cotton dyestuffs may dye or color the regenerated cellulose our copending application Serial No.

Great Britain April 22, 388,262.

ticular way of dyeing with these dyes, following the general directions of the above identilied patents, the procedure is as follows: A dyebath is made up from 3000 parts of water and 2 parts of the dyestuff obtained by combllllllgQlG parts of tetrazotized 4: 4'-diaminodiphenyl sulphide with 138 parts of salicylic acid and 315 parts of Q-phenylamino-S-naphthol-(i-sulphonic acid successively in alkaline solution. 100 parts of viscose silk are entered into the bath cold, after which the bath is heated up to the boil, 30 parts of Glaubers salt are added and dyeing allowed to continue at or near the boil for about hour. Soap may be added to the dyebath if desired. ing obtained has an even level brown shade.

If instead or" the above dyestuif there are used 3 parts of the dyestuff obtained combining 216 parts of tetrazotized 4:e-diaminodiphenyl sulphide with 138 parts of salicylie acid in alkaline solution, and then with the aminoazo compound obtained by combining 138 parts of diazotized p-nitroaniline with 319 parts of 1-amino-8-naphthol-3z6- disulphonic acid in mineral acid in the known way, the regenerated cellulose silk is dyed an even level dark green shade.

In the table given below we set forth many typical compounds of the broad class which we have found suitable for use in the presout process of dyeing regenerated cellulose materials in even level shades. In the production of these compounds the coupling with the aminonaphthol sulphonic acids or their derivatives is effected in an alkaline medium unless otherwise stated. These dyestuffs may be applied to regenerated eel lulose materials in the manner given above or in any other suitable way. In the last column of the table we set forth the shade on viscose silk obtained by the application thereto of these dyes.

lose materials dyestuflt's having the general formula Diamine First coupling component Second coupling component shade g 4:4'-diamino-diplienyll-amino-8-naphthol-4-sulphonic acid 1-am n0-8-naphth0l-4-sulphonic acid Reddisli-violet.

nionosul hide.

Dlttof 2-plienylamiiio-5-naplitliol-7-sulphonic 2-pheny1amin0-5iiaphthol-7-su1phonic acid. Bluish-red.

aci Salicylic acid d itt0 Red. 2-3mi[10-5-llaphthol-7 sulphonic ac 2-amino-5-naphthol-7-sulphon1o-acid Scarlet, 1 (2:5 dichloro 4 sulphophenyl) 3 2-plienylammo-S-naphthoLfi-eulphomc acid Yellowisli-brown.

methyl-5-pyrazoione (acid coupled). 1- phenyl-3-methyl-5-pyrazolone (acid 2-am1110-5-naphthol-7-sulplionic acid Scarlet.

nffd i ith S-hydroxy-2-naphthyl-glycinegi-suiplionic acid. Brown. Ditto l-(4-sulphophenyl)-3-methy1-5-pylflzo1one 2-amino-8-naphthol-6-sulphonic acid Brown. Ditto. itto ..ditto(acid coupled) Orange-red. Dlt 'tto 2-pheiiylamiiio-8-naphthol-6-sulplionic acid Brown.

(acid coupled). Ditto Salicylic acid 2-a ini -g3ll8Dh h0l-6-S11lP1101116 acid (acid Scarlet:

coupe Ditto ditto Z-acetyl'amino-8-naplithol-6rsulplionic acid Scarlet. 4:4-diamixio-diphenyl- 2-amino-5-naphthol-7-sulphonic acid. Z-amiilo-5-i1ephth0l-7-sulphomc acid Scarlet.

Digtii fi 2-amino 8-naplithol-fi-sulplionic aoid 2-ami 1 -8-naphthol-6-suluhonic acid Violet-brown, 4:4'-diamino-diphenylditto dit Maroon.

trlsulphide.

Ditto 1-plienyl-3-methyl-5-pyrazolone (acid 8-hydr0xy-2-naplithyl-glyciiiefi-sulphonicacid. Light-brown,

1 1-g iiifiiliophenyl)-3-methyl-5-pyrazolone 2-aniinp-g3naphtliol-6-sulphonic acid (acid Yellow.

coup e d 2-amino-5-naphtlio1-7-sulphonic acid Orange, 2'111'Xylylflmin -8-n3l h0l-6-l11ph0i1i0BC1d Brown, Z-amino-8-naphtliol6-sulphonic acid (acid 2-aminot-naphthol-fisulphonic acid- (acid Maroon.

coupled) coupled) What we claim and desire to secure by Letters Patent is: I i

1. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestufli's having the general wherein It represents a divalent phenyl residue, w is an integer greater than 0 and less than 4 and R represents a coupling component of the benzene, naphthyl or pyrazoleneseries, and R represents an aminonaphthol sulphonic acid, and in which the N =N groups are connected to the phenyl residue in the position para to the S atom.

2. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestufishaving the general formula wherein m is an integer greater than 0 and less than 4, R represents a coupling component of the benzene, naphthyl or pyrazolone series, and R represents a coupled 2 :.8-aminonaphthol sulphonic acid.

7 3. The process of dyeing regenerated cellulose materials in even level shades which comprises'applying to said regenerated celluwherein m is'an integer greater than 0 and less than 4, R represents a coupled salicyclic acid and R represents an aminonaphthol sulphonic acid:

4. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestuffs having the general formula wherein m is an integer greater than 0 and less than 4,11 represents a coupled salicyclic acid and R5 represents a coupled 2: 8aminonaphthol sulphonic acid.

5. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestufi's having the general formula wherein R represents a coupled salicylic acid and R represents a coupled aminonaphthol sulphonic acid.

6. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestuffshaving the general formula wherein R, represents a coupled salicylic acid and R represents a coupled 2: S-aminonaphthol sulphonic acid.

7. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestuffs having the general formula wherein R represents a coupled salicylic acid and'R represents a coupled Q-phenylamino- 8-naphthol-6-sulphonic acid.

8. Regenerated cellulose materials dyed witlh the dyestuffs having the general formu a wherein at is an integer greater than 0 and less than 4, R represents a coupling component of the benzene, naphthyl or pyrazolone series, and R represents a coupled 2: 8- aminonaphthol sulphonic acid, the said dyed regenerated cellulose materials having even level shades.

10. Regenerated cellulose materials dyed witlh the dyestuffs having the general formu a wherein ais an integer greater than 0 and less than 4, R represents a coupled salicylic acid and R represents an aminonaphthol sulphonic acid, the said dyed regenerated cellulose materials having even level shades.

11. Regenerated cellulose materials dyed witlh the dyestuffs having the general formu awherein a: is an integer greater than 0 and less than 4, R represents a coupled salicylic acid and R represents a coupled 2: 8-am1no- 12. Regenerated cellulose materials dyed witlh the dyestuffs having the general formu a wherein R represents a coupled salicylic acid and R represents a coupled aminonaphthol sulphonic acid, the said regenerated cellulose materials having even level shades.-

13. Regenerated cellulose materials dyed with the dyestuffs having the general formula wherein R represents a coupled salicylic acid and R represents a coupled 2: 8-a1ninonaphthol sulphonic acid, the said regenerated cellulose materials having even level shades.

14. Regenerated cellulose materials dyed in even level shades With the dyestuffs having the formula wherein R represents a coupled salicylic acid and R represents a coupled Q-phenyI-amino- 8-napthol-6-sulphonic acid, the said regenerated cellulose materials having even level shades.

.15. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to .said regenerated cellulose materials dyestuffs having the general formula wherein m is an integer greater than 0 and less than 4, R represents an aminonaphthol sulphonic acid and R represents a coupling component selected from a group consisting of the benzene, naphthalene and pyrazolone series.

16. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestuffs having the general formula nr-mnOsro-ihN-m wherein an is an integer greater than 0 and less than 4, R represents an aminonaphthol sulphonic acid and R represents a coupled salicylic acid or one of the following structures on NH:

HO; NHR NHR H AOsH naphthol sulphonic acid, the said regenerated cellulose materials having even level shades.

wherein R represents hydrogen, an acyl or a benzene residue.

17. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestuffs having the general formula wherein m is an integer greater than Oand less than 4, R represents an aminonaphthol sulphonicacid and R represents a coupled 2-amino-8-naphthol-6-sulphonic acid, the amino group of which may be substituted With an acyl group or a benzene residue.

18. The process of dyeing regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materials dyestufis having the general formula HO;S NHR wherein R represents an aminonap'hthol sulphonic acid and R represents a coupled salicyclic acid or one of the following structures wherein R represent hydrogen, an acyl or a benzene residue.

19. The process of dyeing. regenerated cellulose materials in even level shades which comprises applying to said regenerated cellulose materialsidyestufis having the general formula wherein R represents an aminonaphthol sulphonic acid and R represents a coupled Q-amino-S-naphthol-fi-sulphonic acid, the amino group of which may be substituted with an acyl group or a benzene residue.

20. Regenerated cellulose materials dyed OH HO: NHB

with dyestufi's having the general formula wherein a: is an integer greater than 0 and less than 4, R represents an aminonaphthol sulphonic acid and R represents a coupling component selected from a group consisting of the benzene, naphthalene and pyrazolone series, the said dyed regenerated cellulose materials having even level shades.

21. Regenerated cellulose materials dyed with the dyestuffs having the general formula m-NmOsOnzN-m wherein a: is an integer greater than 0 and less than 4, R represents an aminonaphthol sulphonic acid and R represents a coupled salicylic acid or one of the following structures on 011 NH:

NHR

Ho,s-

wherein R represents hydrogen, an acyl or a benzene residue, the said dyed regenerated cellulose materials having even level shades.

22. Regenerated cellulose materials dyed OH NH:

with the dyestuffs having the general formula wherein R represents an 'aminonaphthol sulphonic acid and R, represents a coupled salicylic acid or one of the following 'structures.

0H NH:

wherein R represents hydrogen, an acyl or a benzene residue, the said dyed regenerated cellulose materials having even level shades.

24. Regenerated cellulose materials dyed with the dyestuffs having the general formula wherein R represents an aminonaphthol sulphonic acid and R represents a coupled 2-amino-8-naphthol-6-sulphonic acid, the amino group of which may be substituted with an acyl group or a benzene residue.

25. Regenerated cellulose materials dyed with a dyestufl? having the probable formula wherein R represents a coupled 2-amino-8-' naphthol-G-sulphonic acid. I

26. Regenerated cellulose materials dyed with a dye-stufi' having the probable formula wherein R represents a coupled 2-amino-- 5-naphthol-7-sulphonic acid.

In testimony whereof we affix our signatures.

RAINALD BRIGHTMAN. PERCY CHORLEY. 

